Journal of Geosciences, 59 (2014), 99–114

DOI: 10.3190/jgeosci.163

Review

Oxidation–hydration weathering of uraninite: the current
state-of-knowledge
Jakub Plášil
Institute of Physics, Academy of Sciences of the Czech Republic v.v.i, Na Slovance 2, 182 21, Prague 8, Czech Republic; plasil@fzu.cz
Oxidation–hydration weathering of uraninite, the most common U-bearing mineral in nature, comprises various physical and chemical processes that lead to the destruction of the fluorite-type structure of uraninite where U is present
as tetravalent. This results in replacement of uraninite by weathering products containing U in hexavalent form, i.e. as
uranyl ion, UO22+. The final assemblage of the weathering products, uranyl minerals, and their compositions dependon the various factors, namely the composition of the primary minerals and percolating oxidizing fluids that cause thealteration. The knowledge of such processes and stabilities of the uranium minerals is of the great interest namely due
to demand for U as the energy source. During the past decade there has been substantial progress in understanding themineralogy, crystallography and thermodynamics of uranyl minerals and thus a substantially improved understandingof the weathering processes themselves. This review aims to summarize the state-of-art of the current knowledge on
uranium-related topics as well and identify some of the important questions that remain unanswered.
The following text is dedicated to Jiří Čejka on occasion of his 85th birthday anniversary. Jiří greatly contributed not
only to the spectroscopy and mineralogy of uranyl minerals, but also to the questions pertaining their origin and stability.
Many important issues were addressed, even if briefly, in the pioneering book “Secondary Uranium Minerals” by Čejka
and Urbanec (1990) which has served, for a long-time, as a guide for beginning uranium mineralogists.
Keywords: weathering of uraninite, paragenetic sequence, bond-valence theory, uranyl–oxide minerals, radiogenic lead, thermodynamics
Received: 10 December 2013; accepted: 16 March 2014; handling editor: J. Sejkora

1. Introduction
Uraninite, ideally cubic (Fm3̄m) UO2, however, never occurs in Nature as stoichiometrically pure U4+ oxide, butrather as UO2+x (where x = 0–0.25) (Janeczek and Ewing
1992). Most commonly is uraninite found in the colomorph
form known as “pitchblende” (Fig. 1a), which undergoes
rapid alteration in a humid, oxidizing environment. The
corrosion process is described as “oxidation–hydration
weathering”. This process leads to the decomposition of theuraninite structure, primarily via the oxidation of U4+ to U6+,
which is, in general, incompatible with the uraninite structure. Moreover it includes also leaching or replacement of
uraninite by the younger minerals – supergene weathering
products, usually containing U6+ in their crystal structures.
The leaching of uraninite leads to the release of U6+, as
the uranyl ion (UO2)2+, into the solution, where it exists
as aquatic anionic complexes (depending on the pH of thesolution and concentration of dissolved anions). In weakly
acidic to weakly alkaline solutions (matching properties ofmost groundwaters) the uranyl carbonate complexes arethermodynamically favored when CO2 is a dominant aqueous species. The most abundant aqueous species are thenuranyl monocarbonate, [(UO2)(CO3)]0, uranyl dicarbonate,[(UO2)(CO3)2]2– and uranyl tricarbonate, [(UO2)(CO3)3]4–,complexes at pK values of 5.5, 7 and 9, respectively (Lang-muir 1978). In the form of aquatic anionic complexes, theU6+ ion is very mobile and can migrate for a long distance.
Therefore many uranyl minerals may be found without
any obvious spatial relation to the primary ore (Fig. 1b).
The in-situ alteration products replacing directly the uraninite aggregates are known mostly as “gummites” (Fig.
1c). This obsolete, however still useful name, is used for
massive, often layered and microcrystalline, mixtures ofthe diverse compositions (described for the first time by
Frondel 1956) replacing uraninite. The proportion of themineral components in “gummites” depends on a variety
of factors e.g., the rate of groundwater percolation and its
chemical composition, the age of uraninite and its chemicalcomposition (e.g., Pb content). Studying the mechanisms
and products of the oxidation–hydration weathering of
uraninite is important for better understanding of both thegenesis of uranium deposits (particularly important for mineral exploration) and dissolution, transport and retardation/
immobilization of environmentally harmful elements suchas uranium, other radionuclides, Se and Pb. During the last
decades an impressive step forward has been taken in the
many new studies that have added to the knowledge of thecrystal chemistry of uranium, the thermodynamics of theuranyl minerals, and the important physical processes connected to the weathering (dissolution, precipitation, etc.).
This paper is not meant to be an exhaustive review of all of
www.jgeosci.org

Jakub Plášil

(a)

(b)

pitchblende(c)Fig. 1a – Uraninite in the form of “pitchblende” in calcite gangue.
The pit #15, Příbram uranium deposit. The width of the photograph(field-of-view, FOV) 15 cm, photo P. Škácha. b – Efflorescence ofschröckingerite (showing greenish fluorescence in the UV lamp light)
on the wall of the mining adit without any significant primary uranium
mineralization. Svornost mine, Jáchymov; photo P. Škácha. c – “Gummite” – residual uraninite (blackish) being replaced by orange masuyite.
Dump of the Rovnost mine, Jáchymov. The width of the sample is 4 cm.
Photo P. Škácha.

the mentioned issues, but it is rather a brief summary of thecurrent knowledge on uranium-related topics (mainly fromthe mineralogical point of the view). Moreover, it aims toidentify several still unclosed gaps in the knowledge of
uranium minerals.

1.1. Uraninite and spent nuclear fuelThe moving power for the studies undertaken namely in
1990s was the rising energy consumption and related demand to use uranium as an energy source. This has beenconnected with an increased pressure for the disposal of
spent nuclear fuel (SNF), which consists of irradiatedUO2, in underground geologic repositories (Wronkiewicz
et al. 1992; Ewing 1993; Janeczek et al. 1996). Long-term
tests of the stability and durability of SNF exposed to theweathering (air, mineralized solutions and/or increased
temperature), as may happen in underground repositories
when engineered barriers fail, have been undertaken(Wronkiewicz et al. 1992, 1996). Numerous studies onnatural uraninite as an analogue for SNF (Janeczek et
al. 1996) were undertaken with the particular interest
both in physico-chemical processes that occur during
100

the alteration (e.g., Finch and Ewing 1992; Isobe et al.
1992; Pearcy et al. 1994; Finch et al. 1996; Murakami etal. 1997; Schindler and Hawthorne 2004; Schindler andPutnis 2004; Schindler et al. 2004a, b, c; Deditius et al.
2007a, b, 2008; Schindler et al. 2011; Forbes et al. 2011)
and in the formation of supergene phases as the concentrators of the elements of the interest – uranium and possible
fission products (such as Pu, Sr, Np) (Burns et al. 1997a,b; Burns 1999a; Burns and Hill 2000; Cahill and Burns
2000; Li and Burns 2001; Burns and Li 2002; Burns etal. 2004; Klingensmith and Burns 2007; Klingensmith etal. 2007). The long-term tests (Wronkiewicz et al. 1992,
1996) showed that the alteration mechanisms for nuclear
fuel and uraninite lead to the same weathering products.

2. Uranyl minerals – products of weathereduraninite

2.1. Mineralogy and crystallography
During the last decades there has been a substantial
increase in the knowledge of the mineralogy and crystal

Weathering of uraninite

(a)
(b)
(b)

(c)

(d)

(f)

(g)

(d)

(e)

0.71

0.44
50 μm

0.53

0.44

1.59
1.64

1.64

1.67

1.67

Fig. 2 Ball-and-stick representation of the uranyl ion, UO22+ (a), tetragonal (b), pentagonal (c) and hexagonal (d) bipyramids, as well as theircorresponding polyhedral representations (e–g) with the bond-valence sums (in valence units) incident upon each vertex owing to the U 6+–O bondwithin the polyhedra (values from Burns et al. 1997a).

chemistry of uranium, especially of phases containing U6+ (Burns et al. 1996, 1997a; Burns 1999b, 2005;
Krivovichev and Plášil 2013). This fact was possible dueto the increasing capabilities of the analytical techniques,
namely in the field of X-ray diffraction and CCD imaging techniques (Burns 1998a) used as a tool for crystal
structure determination.
The mineralogy of hexavalent uranium is extremely
diverse due to the specific electronic properties of U
in such a high-valence state, which leads to the highly
anisotropic coordination polyhedra around the U6+ cation.
The U6+ exists as the uranyl ion UO22+, where the two
O atoms (OUr atoms) are strongly bonded (a triple-bond)in a nearly-linear, dumbbell-like (Fig. 2a), geometry to acentral U atom at the distances ranging most commonlyfrom ~1.78 to ~1.81 Å (Burns et al. 1997a), dependingon the type of the coordination polyhedra. The physicochemical properties of the uranyl ion are unique, and thus
it cannot be easily substituted by any other high-valence
cation. To satisfy the bond-valence requirements, theuranyl ion needs to be coordinated to more ligands, usually O atoms (Oeq). These additional ligands are arranged
at relatively long distances from the central U6+ at theequatorial vertices of the uranyl tetragonal (4 equatorial
ligands at the distance ~2.30 Å) (Fig. 2b), pentagonal(5 ligands, ~2.37 Å) (Fig. 2c) or hexagonal (6 ligands,~2.46 Å) (Fig. 2d) bipyramids, with OUr atoms at thevertices (Burns et al. 1997a; Burns 2005). The ligand
atoms are usually undersaturated in terms of their bondvalence requirements (Fig. 2e–g) and tend to polymerize,
thus forming clusters, chains, sheets or three-dimensionalframeworks with incorporated additional cations, mostcommonly coordinated in tetrahedral anionic groups(e.g. SO42–, PO43–, AsO43–, SiO44–). In order to simplify
and classify the crystal structures of uranyl minerals, thestructural hierarchy of the structures was developed basedon the topologies of the basic structure units – uranyl
anion topologies (Burns et al. 1996; Burns 1999b, 2005)
following the general idea of Hawthorne (1983, 1994)
and in accord with the bond-valence theory (Brown
1981, 2002, 2009). The topologies of the structural units(Fig. 3a) of uranyl minerals and compounds, which are
the “consolidated” parts of the structures that containcations of higher valence and have anionic character, arerepresented by corresponding graphs. The anion topology
can be derived using the following rules (Burns 2007):(1) only Oeq atoms are considered that are bonded to two
or more cations within the layer, (2) the Oeq atoms thatare separated by less than 3.5 Å are connected by lines(Fig. 3b), (3) all atoms are removed from considerationand the resulting tiling is projected onto a 2-D plane(Fig. 3c). Burns (2005) presented 368 inorganic crystal
structures containing U6+, of which 89 were minerals.
Based on this analysis, eight were based upon isolated101

Jakub Plášil

(a)
a

(b)

(c)

b

c

Fig. 3 The sheet of polyhedra in the structure of γ-(UO2)(OH)2 (a), square-grid consisting of equatorial O atoms (b) and the idealized graph of its(autunite) topology (c).

polyhedra, 43 upon finite clusters, 57 upon chains, 204(!)
upon sheets, and 56 upon frameworks of polyhedra. The
most recent overview on the mineralogy and crystallography of uranium has been given by Krivovichev
and Plášil (2013). Many new uranium minerals with adiverse chemical composition and fascinating structures
have been described in the past few years (e.g., Sejkora
and Čejka 2007; Mills et al. 2008; Walenta et al. 2009;
Meisser et al. 2010; Kampf et al. 2010; Plášil et al.
2010a; Brugger et al. 2011; Plášil et al. 2011a, b; Pekov
et al. 2012a, b; Plášil et al. 2012a, b, c; Walenta andTheye 2012; Kampf et al. 2013; Pekov et al. 2013; Plášil
et al. 2013a, b, c). Nowadays, more than 260 minerals (!)
are known to contain U in their crystal structures (not allof the U-structures are known).

2.2. The role of uranyl-oxide–hydroxy–hydrates
in the evolution of uraninite(SNF)-weathering paragenetic sequences
and the role of radiogenic Pb
Uranyl-oxide–hydroxy–hydrate minerals play a key rolein alteration of uraninite as the very initial alteration
phases in the weathering paragenetic sequences (Finch
and Ewing 1992; Finch and Murakami 1999; Krivovichev
and Plášil 2013). There are numerous research papers devoted to the issue of the uranyl–oxide minerals and theirsignificance during the uraninite weathering (e.g., Finch
and Ewing 1992; Finch et al. 1996; Burns 1997; Burns etal. 1997b; Burns 1998b, c; Finch et al. 1998; Schindler
and Hawthorne 2004; Brugger et al. 2004; Hazen et al.
2009; Brugger et al. 2011). Several different alteration
pathways are generally accepted. The very beginningphase of the alteration is common for distinct pathways: uraninite is altered first to the metallic-cation-freemineral, such as ianthinite, [U 4+(UO2)4O6(OH)4(H2O)4]102(H2O)5 (Burns et al. 1997c) and further to schoepite,[(UO2)8O2(OH)12](H2O)12 (Finch et al. 1996) (Fig. 4).
Schoepite and the closely-related phases, such as meta­schoepite, (UO2)(OH) (Weller et al. 2000) and paulscherrerite (Brugger et al. 2011), represent a quite complex
suite of minerals related by the dehydration processes(Finch et al. 1998). During the subsequent alteration, acomplex suite of uranyl-oxide–hydroxy–hydrate minerals is developed. The overview of the known oxide–hydroxy–hydrate minerals is given in Tab. 1, along with
their important crystal-chemical features. A two-stage
weathering process was identified by Finch and Ewing(1992):a) When the mineral system contains radiogenic Pb(its source being the “old uraninite”), a suite of Pb-containing uranyl–oxide minerals evolves during thealteration that is characterized by an increasing molar
ratio of Pb2+/H2O as the function of the progressively

Sch
Py

Fig. 4 Ianthinite (violet blackish) partly altered to schoepite (Sch;yellow) growing on pyrite (Py) grains in the barite gangue. Menzenschwand uranium deposit, Schwarzwald (Germany). FOV 3.4 mm,
photo P. Škácha.

Weathering of uraninite

Tab. 1 Overview of the known uranyl-oxide–hydroxy–hydrate minerals or mineral-related synthetic materials with details on the stereochemical
properties of their structural units
Mineralschoepite
metaschoepite (synth.)paulscherrerite
Na-metaschoepite (synth.)heisenbergite
becquerelitecompreignacite
billietite
rameauite
vandendriesscheite
fourmarierite
agrinierite
richetitemasuyiteprotasite
curitesayritewölsendorfite
spriggite

Formula[(UO2)8O2(OH)12](H2O)12[(UO2)4O(OH)6](H2O)5
UO2(OH)2
Na[(UO2)4O2(OH)5](H2O)5(UO2)(OH)2(H2O)[7]
Ca(H2O)4[(UO2)3O2(OH)3]2(H2O)4[7]
K2(H2O)3[(UO2)3O2(OH)3]2(H2O)4[10]
Ba(H2O)4[(UO2)3O2(OH)3]2(H2O)3
K2Ca[(UO2)6O4(OH)6](H2O)6[9]
Pb1[8]Pb0.57(H2O)5[(UO2)10O6(OH)11](H2O)6[9]
Pb(H2O)2[(UO2)4O3(OH)4](H2O)2[8]
K2[9](Ca,Sr)(H2O)5[(UO2)3O3(OH)2]2[6]
Mx[8.4]Pb8.57(H2O)31[(UO2)18O18(OH)12](H2O)10[10]
Pb(H2O)3[(UO2)3O3(OH)2][10]
Ba2(H2O)3[(UO2)3O3(OH)2][9]
Pb3(H2O)2[(UO2)8O8(OH)6][9]
Pb2(H2O)4[(UO2)5O6(OH)2][8.15](Pb6.2Ba0.4)(H2O)10[(UO2)14O19(OH)4](H2O)2[8.4]
Pb3[(UO2)6O8(OH)2](H2O)3

Structural unit
CDA [vu][(UO2)8O2(OH)12]0
0.08[(UO2)4O(OH)6]0
0.08[(UO2)(OH)2]0
0.10[(UO2)4O2(OH)5]1–
0.13[(UO2)(OH)2]0
0.16[(UO2)3O2(OH)3]21–
0.145[(UO2)3O2(OH)3]21–
0.145[(UO2)3O2(OH)3]21–
0.145[(UO2)3O2(OH)3]21–
0.145[(UO2)10O6(OH)11]3–
0.14[(UO2)4O3(OH)4]2–
0.19[(UO2)3O3(OH)2]2–
0.22[(UO2)3O3(OH)2]2–
0.22[(UO2)3O3(OH)2]2–
0.22[(UO2)3O3(OH)2]2–
0.22[(UO2)8O8(OH)6]6–
0.24[(UO2)5O6(OH)2]4–
0.24[(UO2)14O19(OH)4]14–
0.29[(UO2)6O8(OH)2]6–
0.29

Reference
Finch et al. (1996)
Weller et al. (2000)
Brugger et al. (2011)
Klingensmith et al. (2007)
Walenta and Theye (2012)
Burns and Li (2002)
Burns (1998c)
Finch et al. (2006)
Cesbron et al. (1972)
Burns (1997)
Li and Burns (2000b)
Cahill and Burns (2000)
Burns (1998b)
Burns and Hanchar (1999)
Pagoaga et al. (1987)
Li and Burns (2000a)
Piret et al. (1983)
Burns (1999c)
Brugger et al. (2004)

CDA – Charge Deficiency per Anion; calculated as the effective charge of the structural unit divided by the number of anions in the structural unit.
The effective charge is the formal charge plus the charge contributed by the (H)-bonds in the structural unit = n × 0.2.

increasing degree of alteration (with increasing time).
Such a pathway is represented by the following paragenetic sequence: schoepite → vandendriesscheite→ fourmarierite → masuyite → sayrite → curite →wölsendorfite → richetite → spriggite.
b) The system that does not contain radiogenic Pb (derived from the “young uraninite”) is again characterized by the increasing molar ratio of Me (a metal
cation) to H2O with increasing degree of alteration. It
is represented by the paragenetic sequence: schoepite→ becquerelite (Ca2+), billietite (Ba2+), compreignacite(K+) → agriniérite (Sr2+) and protasite (Ba2+) → clarkeite (Na+).
There is a relation between the molecular proportionof water and content of metal cations in the uranyl–oxideminerals (Fig. 5). This was first documented by Finch andEwing (1992), who showed that the changing ratio corresponds closely to the degree of alteration. The youngest
alteration phases (the first formed from uraninite), suchas schoepite, contain large amounts of H2O and a little orno metal cations. With continuing alteration, the ratio between H2O and Me decreases. Schindler and Hawthorne(2001) studied the paragenetic relations of borates examining the stereochemical properties of their structures(so called “the bond-valence approach”). They showedthat there is a reasonable relation between the structuralconfiguration of the hydrated oxysalts and the propertiesof the solution (pH and activity of dissolved elements)from which they precipitate. The measure related to the
crystal structure they introduced is called the “Charge
Deficiency per Anion” (CDA) and is given in valence

units. The CDA is defined as the average bond-valence
per O atom contributed by the interstitial species andadjacent structural units. This value correlates strongly
with the average O-coordination number of the structuralunit (which correlates extensively with the Lewis basicityof the structural unit), and hence it plays a crucial role in
the predictive power of the crystal-chemical properties ofthese phases. For borate minerals, Schindler et al. (2001)
documented that the borate structural units with the lower
CDA values crystallize from the solution of the lower pH
than the species with high CDA values. Using the same
approach, Schindler and Hawthorne (2004) examined theuranyl-oxide–hydroxy–hydrates. They concluded thatthe restricted range in Lewis basicity, characterizing thestructural units of uranyl-oxide–hydroxy–hydrates, is reflected by their narrow stability field. Further they provided a priori deduction of the relative stability fields of theuranyl-oxide–hydroxy–hydrates with respect to changing
pH and composition (contents of metal cations) of thesolution. Along with the increasing pH, there is a change
in topologies of the structural units of uranyl-oxide–hydroxy–hydrates from the lower degree of polymerization(in schoepite) to higher degree of polymerization, i.e.
topologies containing pentagonal and hexagonal bipyramids and fewer unoccupied triangles. The CDA values
for known uranyl-oxide–hydroxy–hydrate minerals are
given in Tab. 1. The dependence of CDA on the molar
proportion of H2O in these minerals (as the function ofalteration degree) is illustrated in Fig. 5. Krivovichev andPlášil (2013) discussed the paragenetic scheme presented
originally by Belova (1975, 2000) (see Fig. 6). This103

Jakub Plášil

0.30

CDA
0.25

mol Me

0.20

0.15

0.10

0.05

Alteration (time)schoepite
metaschoepite
heisenbergite

0.00

CDA
0.2

0.3

0.4

0.5

0.6

0.7

0.8

mol H2O
Fig. 5 Composition of uranyl-oxide–hydroxy–hydrate minerals as a function of molecular proportions of H 2O and Me (Me = metal cations). The
solid black line represents regression trend (R2 = 0.61) between molecular proportion of H2O and the Charge-Deficiency per Anion (CDA) value(in valence units). The symbols for CDA are omitted for clarity. The scale of the y axis is the same for both datasets.

scheme represents another perspective on this complex
system that leads to new ideas, summarized below.
1. During the initial stage, the alteration of primaryuranium minerals takes place before the oxidation of
sulfides at neutral or alkaline conditions caused by thepresence of vein carbonates and alkali elements. This
stage is dominated by the presence of uranyl oxideminerals (usually forming gummite) and corresponds
to the early stages described by Finch and Ewing(1992). Uranyl carbonates are leached out due to theundersaturated percolating water (e.g. with low pCO2),and U6+ can be released into the solution in the form of
uranyl–carbonate complexes. This leads to the precipitation of uranyl–carbonate minerals, such as metal-freecarbonates as rutherfordine, (UO2)(CO3) (Fig. 7a) or
containing monovalent or divalent metal cations asgrimselite, K3Na[(UO2)(CO3)3](H2O) (Fig. 7b) or bay­leyite, Mg2[(UO2)(CO3)3](H2O)18 (Fig. 7c), respectively. Noteworthy, uranyl carbonates can form a part of
the “gummites”. This was documented for example
in case of the Pb2+-containing uranyl carbonate widenmannite (Plášil et al. 2010b) or monocarbonate
rutherfordine (Plášil et al. 2006). The occurrence of theunique, U5+-bearing carbonate wyartite, CaU5+(UO2)2(CO3)O4(OH)(H2O)7 (Burns and Finch 1999) (Fig. 7d)
is also interesting, as is its position in the paragenetic
scheme of the early alteration products after uraninite
weathering. In the CO2–UO22+-bearing solutions after104

the dissolution of gangue carbonates, the UO22+ ion
can be transported in the form of the aqua–carbonate
complexes over long distances (Langmuir 1978). Fromsuch solutions in contact with the SO 42–-containing
waters (derived from dissolved oxidized sulfides),minerals like schröckingerite, NaCa 3[(UO 2)(CO 3)3]
(SO4)F(H2O)10 (Mereiter 1986) can precipitate. Schröckingerite is one of the most widespread secondary
uranyl minerals occurring in Nature; however, it isusually rather inconspicuous, forming most commonly
efflorescence on the walls of the mining adits (Fig. 1b)(see also e.g., Klomínský et al. 2013). In the end of
this stage uranyl silicate minerals may occur due tothe increase in the Si4+ activity mainly released fromthe surrounding rocks due to proceeding alteration.
2. At the second stage, simultaneous massive alterationof uranium and sulfide minerals takes place. This stage
begins with the oxidative weathering of basic sulfides(pyrite, marcasite, chalcopyrite, pyrrhotite and arsenopyrite), when the vein carbonates have been alreadyleached out and can no longer buffer the solution
composition. This results in the formation of the freesulfuric acid, as well as other acids, leading to acidic
conditions. This results in the formation of uranyl
sulfate minerals that may occur as minor alteration
phases during the post-mining processes, known as
the Acid-Mine Drainage (AMD) (e.g., Brugger et al.
2003) (Fig. 7e).

Weathering of uraninite

Fig. 6 Schematic representation of the paragenetic sequence of U minerals in oxidation zones of U mineral deposits (after Krivovichev and Plášil
2013).

3. The third stage takes place initially under the weakly
acidic conditions and is represented by the occurrenceof uranyl phosphates (P5+ from the host-rocks), suchas torbernite, Cu[(UO2)(PO4)]2(H2O)12, and arsenates(As5+ from the residue after dissolved arsenides), as
zeunerite, Cu[(UO2)(AsO4)]2(H2O)12.
105

Jakub Plášil

50 μm

(c)

(d)

(e)

(f)

Fig. 7 Supergene uranium minerals. a – Uranyl carbonate rutherfordine (acicular) growing on silicate soddyite (short prismatic orange) from the
Shinkolobwe mine, Congo. FOV 2.3 mm. b – Long-prismatic crystals of uranyl carbonate grimselite from Jáchymov. FOV 3.8 mm. c – Blocky
aggregates of uranyl carbonate mineral bayleite from Jáchymov. FOV 2.5 mm. d – A rare uranyl carbonate mineral wyartite, containing U5+.
Shinkolobwe mine, Congo. FOV 2 mm. e – Typical efflorescence (uranyl sulphate marécottite) formed during acid mining drainage of uranium ina consolidated material on the floor of the mining adit. Jáchymov. f – Uranyl phosphate mineral phosphuranylite (yellow prismatic crystals) in the
typical paragenesis of Fe-oxide–hydroxides forming pseudomorphs after older uranyl phosphate minerals – note the typical bipyramidal crystal of
torbernite. Jáchymov. FOV 3.4 mm. All photos by P. Škácha, except for e (J. Plášil).

4. The change in pH conditions occurs usually whenthe vein sulfide minerals are completely leached out.
The characteristic representatives are minerals of thephosphuranylite group, e.g. phosphuranylite (Fig. 7f),
106

hügellite or dumontite. Such conditions also mightoccur far from the primary source (and sulfides) when
U is remobilized. The buffer agents are then the sur­rounding rocks, i.e. lithological factors.

Weathering of uraninite

5. The last stage in the respective scheme (Fig. 6) is characteristic of alkaline or neutral conditions and involves the U4+-bearing minerals, as reduced backwardly
from UO22+, in situ in the supergene zone. Typically,in such association occur secondary uraninite, coffinite, ningyoite and U4+ phosphates, such as poorly
defined vyacheslavite, U4+(PO4)(OH)·nH2O (Belova
et al. 1984). However, it should be noted that not all
U4+-containing minerals should form under alkaline reducing conditions. For instance, recently documented
unique association of secondary U4+-bearing arsenate
and sulfate minerals, štěpite, U(AsO3OH)2(H2O)4 (Plášil et al. 2013a) or běhounekite, U(SO4)2(H2O)4 (Plášil
et al. 2011), formed from extremely acid solutions (pH~0) derived from As-rich AMD at the Geschieber veinin Jáchymov.
Besides these general trends during uraninite weathering, it should be noted that the particular evolutionary path of the given mineral weathering association
depends on the very local characteristics. These include
the regional tectonics at the first place, geochemistry of
the host-rocks, composition of primary ore and finally,
the compositional evolution of the percolating groundwater. Not unusual is also a cyclic character of the alteration with alternating occurrence (dominance) of e.g.,uranyl phosphates and silicates, forming pseudomorphs
or growing over one another. A nice contribution to theknowledge of the mechanisms of weathering of uranium
deposits was published recently by Göb et al. (2013).
Their study was focused on the remobilization of U
and REE in the supergene zones of the Menzenschwand
U-deposit in Schwarzwald (Black Forest Mts.), southwestern Germany, using ICP-MS analysis of the primaryand supergene minerals, water geochemistry and geochemical modelling. The conclusions of this case study
are probably of general validity, as shown by examples
from various other uranium deposits. The sources for the
REE in the system can be either uraninite and fluorite(like in some of the deposits in Black Forest Mts.) or
the surrounding rocks. Based on the systematic study of
PAAS-normalized REE patterns (Post-Archean Australian
Sedimentary rocks), Göb et al. (2013) concluded thaturanyl silicates formed under more reducing conditions(and lower pH) than uranyl phosphates and arsenates,
documented with the lack of Ce3+ anomalies in studied
uranyl silicates. The REE patterns of uranyl phosphates
and arsenates studied resemble those of the mine-water
samples, suggesting a uranium and REE transport fromthe source before crystallization. On the other hand, theREE patterns of uranyl silicates are similar to those ofhydrothermal uraninites, suggesting the close origin of
the supergene uranyl silicates and the primary ore (restricted redistribution and fractionation due to long-scalemigration). The key-role for the pH–Eh changes plays

the vein sulfide – its oxidation leads to the consumptionof O2 (thus the decrease of pO2), drop in pH (due to increase in acid H+) and increase of Fe3+ in the system. The
transport or migration of REE is connected with mobile
fluorine complexes. Thus there is a need for a source ofF in order to maintain its high concentrations. In the caseof Menzenschwand deposit (Göb et al. 2013), the likely
source of REE was fluorite and the release of REE led tothe crystallization of REE-phosphates (e.g. churchite-Y)at the late stages of the weathering. The precipitation of
REE-phosphates, relatively younger than U-phosphates,
is documented from various Variscan hydrothermalvein deposits. Illustrative examples represent Jáchymov(Ondruš et al. 1997) or Medvědín (Plášil et al. 2009)
deposits in Bohemian Massif.
The role of radiogenic Pb during the alteration of
uraninite is thought to be significant, at least for the decomposition of uraninite structure, as was documented by
Janeczek and Ewing (1995), since Pb2+ is incompatible
with fluorite-type structure at concentrations greater thana few percent. If the sulfur activity is high enough, galena(PbS) will form, and the volume of uraninite may change
without any U6+ being released into the solution (Finchand Murakami 1999). If selenium activity is similarly
high, clausthalite (PbSe) and other selenide minerals will
form, as is well documented from the Variscan hydrothermal vein U-deposits. The same authors stated that, in theabsence of sufficient sulfur in the system, uraninite may
exsolve into Pb-rich and Pb-poor domains. In addition thismay lead, along with auto-oxidation and hydration, to theformation of Pb–uranyl-oxide–hydroxy–hydrate minerals,
as typically the early alteration products – vandendriesscheite, [Pb1.6(UO2)10O6(OH)11(H2O)11] and fourmarierite,[Pb1–xO3–2x(UO2)4(OH)4(H2O)8x]. It is important to note thatthese processes are not isolated; it is not unusual that the
specimen containing uraninite and remobilized younger
sulfides or selenides, also contain Pb–uranyl-oxide–hydroxy–hydrate minerals. The process of Pb–U-mineralformation may be enhanced by preferential removal of U6+
as compared with Pb2+ at mineral surfaces by groundwaters. The reason is the high mobility of U6+ compared toPb2+, which results in the formation of Pb-rich minerals
rinds in the residual masses (“gummites”). The Pb-richuranyl-oxide–hydroxy–hydrates may form without highconcentrations of dissolved Pb (Frondel 1958; Finch andEwing 1992; Finch and Murakami 1999).

2.3. Thermodynamics of uranyl minerals
In order to assess, model and predict stabilities of uranyl
minerals formed from primary phases during weathering,
reliable thermodynamic data are necessary. In the past,these data were usually obtained from solubility experiments. A review of the solubility measurements for uranyl
107

Jakub Plášil-2

Uranophane

Soddyitelog [H 4SiO4]-4-6

Metaschoepite

Becquerelite

-8
2

4

6

8

10
2+

12
+

log [Ca /H ]minerals was given by Gorman-Lewis et al. (2008a, b).
Solubility experiments have been undertaken for only
a limited number of uranyl minerals and compounds;
however, the interesting empirical method developed byChen et al. (1999) can be used to derive Gibbs free energies and enthalpies of formation. The method is based
upon contribution of “isolated polyhedra” to the total
Gibbs energy of the formation or enthalpy, respectively.
During the past several years, new thermodynamic datafor uranyl compounds obtained from solution calorimetry measurements have been presented (Kubatko et al.
2005, 2006; Gorman-Lewis et al. 2007, 2009; Shvareva
et al. 2011, 2012; Navrotsky et al. 2013). A comparisonof the thermodynamic values coming from solubility
experiments, estimated using the method of Chen et al.
(1999) and those from solution calorimetry was made by
Shvareva et al. (2012) (Fig. 8). Importantly, the values
obtained empirically, e.g., following the method developed by Chen et al. (1999), are only “rough” estimateswhen compared to more precise measurements. Still theyremain useful in case such experiments cannot be done
(Fig. 8).

3. Gaps, questions and future research

3.1. Mineralogy and crystallography
1. Mineralogical research on the new minerals, as theprimary research goal, is (and should be) still on-go108

14

16

Fig. 8 Stability fields of minerals in the
CaO–SiO2–UO3–H2O system based on
experimental results (blue lines) andempirical model of Chen et al. (1999)(solid black lines). Stability fields derived by Finch and Ewing (1992) are
shown by dashed lines with stabilityof becquerelite (dotted line) estimatedfrom petrographic data. Black points
are composition of groundwater andof J–13 water, respectively, taken fromChen et al. (1999). From Shvareva etal. (2012).

ing. Otherwise, after a certain time, there would not beanything “new” to study. Due to tremendous numberof possible combinations of chemical constituents,
occurring on Earth that can be accommodated in extremely complex structures of U-minerals, the numberof the new uranium mineral species will undoubtedly
increase.
2. The knowledge of the structural properties of U
minerals is crucial for further assessment on the thermodynamic stability and other physical properties.
Actually, there are still many U phases with unknown
crystal structures. Uranyl minerals are usually hydrated oxysalts. There were done only few structure
determinations for uranyl minerals/compounds withdetermined positions of the hydrogen atoms. This isnamely due to the enormous difference in scattering
power of uranium and hydrogen for the X-rays, usedconventionally in the structural crystallography. The
demand for the correct determination of the H2O content and H positions arises from the fact that the roleof H2O in the structures of the hydrated oxysalts, particularly the uranyl minerals, is crucial (e.g., Hawthorne
and Schindler 2008; Schindler and Hawthorne 2008;
Hawthorne and Sokolova 2012; Hawthorne 2012).
3. Many U-containing minerals have unknown crystal
structures (e.g., asselbornite, arsenovanmeerscheite,
astrocyanite-(Ce), blatonite, heisenbergite, joliotite,
paulscherrerite, uranospinite or voglite), and for many
are available only qualitative refinements of theirstructures.

Weathering of uraninite

4. Several uranyl minerals have incorrectly determined
crystal structures (e.g., phosphuranylite, Demartin etal. 1991) or should be discredited as the species completely (e.g., yingjiangite, Chen et al. 1990; Coutinho
and Atencio 2000).

3.2. Weathering processes
1. In order to understand the key role of the processes
taking place during weathering of uraninite, the mostimportant is to decipher the sequence of such processes and redistribution of the elements (REE, U, Pb…)
among primary and secondary minerals, either residual
or newly precipitated, after transport in a solution.
2. Tracking the ages of various uranium mineralizations
is vital in order to assess the sequence of the mineralization and alteration processes. In the past, many
hypogene U-mineralizations were dated by the U–Pb
method (e.g., Holliger 1991; Fayek et al. 2002; Evinset al. 2005; Sharpe and Fayek 2011). However, recently also supergene assemblages were dated using
various techniques (Löfvendahl and Holm 1981; Maas
et al. 2006; Neymark and Amelin 2008; Plášil et al.
2010b; Dill et al. 2010; Birch et al. 2011; Dill et al.
2011, 2013). Timing the supergene U-mineralizations
is also important from another point of the view as it
brings information about paleoclimatic conditions orchanges (e.g., Dill et al. 2010).
3. Important for correct dating is the knowledge about
redistribution of the radiogenic isotopes, especially
radiogenic Pb, in the system. The prevalent opinion
in the literature is that the majority of Pb incorporated in the newly formed Pb–uranyl-oxide minerals isradiogenic (e.g., Finch and Ewing 1992; Finch andMurakami 1999). The case study from the Variscanhydrothermal vein system at Březové Hory deposit inPříbram (Škácha et al. 2009) proved the necessity ofthe detailed research on the fate of both common andradiogenic Pb in hypogene and supergene U minerals.
4. It should be noted that the paragenetic scheme provided by Finch and Ewing (1992) with Finch and Murakami (1999) should be still considered as somewhat
hypothetical, even if many paragenetic sequences
observed in Nature suggest that these are indeed
probable pathways. However, the classification of
uraninites into “old” and “young” groups with regard
to their Pb contents does not provide a fully functional
scheme for understanding, as each uraninite contains
some radiogenic Pb. The amount of the Pb in uraninite(and the possible lack of it) probably results from thedifferent rates of alteration (e.g., variations in the rateof U remobilization).
5. Uranium is very sensitive to the redox conditions,and there is a large difference in mobility of reduced(U4+) and oxidized (U6+) species. Anyway, uranium
occurs also as pentavalent (as e.g. mentioned mineral
wyartite), namely when recurrently reduced from U6+
to U4+. The role of U5+ in the crystalline phases, e.g.
in uraninite itself, has not yet been documented andstudied in detail.
6. The crystal structure of the self-irradiated natural uraninite should be investigated, since the methods used
for studies of synthetic or natural materials designed
for the long-term storage of nuclear waste (e.g., Lianet al. 2009; Zhang et al. 2010; Ewing 2011; Sureda etal. 2011; Deditius et al. 2012) have never been applied
to the natural uraninite. This might help to improve ourunderstanding of the kinetics of the uraninite alteration.
7. Detailed studies on the trace-element distribution, as
for example provided by Göb et al. (2013), combinedwith the information about the age of the individual
mineralization stages, are capable of revealing a more
complete story about the evolution of such weathering
associations.

3.3. Thermodynamics
1. Even though thermodynamic properties of several
uraninite alteration products including uranyl–silicate(e.g., uranophane) or uranyl–oxide minerals, were determined recently, properties of many environmentally
important phases, such as uranyl–sulfates, vanadates
and some phosphates and arsenates, remain unknown
or only poorly defined.
2. The verification of the known thermodynamic data foruranyl minerals needs to be done, e.g. with the same
methodology used in recent studies but with different
standards. Such verifications and cross-checks are very
important, since the thermodynamic data may be used
not only for explanation of geological processes in thepast (e.g., genesis of the certain uranium deposit) but
also of those currently taking place on Earth (e.g., contamination after the U-ore milling and the subsequent
remediation).
Acknowledgements. First of all I would like to thank JiříČejka for his kindness and willingness he is helping theyoung scientists. Furthermore, I would like to acknow­
ledge all the mentors and collaborators with whom I wasable to collaborate since my early studies in Mineralogy as the bachelor student at the Faculty of Science of
the Charles University in Prague. I am grateful to Alex
Navrotsky, Sergey Krivovichev and Rob Raeside, who
granted the permission to reprint figures from their original papers and also to Anatoly V. Kasatkin who provided
a sample from his personal collection for the research.
Pavel Škácha is acknowledged for the high-quality im109

Jakub Plášil

ages of the uranium minerals. This paper benefited fromthe constructive reviews by Rod Ewing and Nicolas
Meisser that helped significantly to improve its quality.
Editorial handling by Jiří Sejkora and editor-in-chiefVojtěch Janoušek are highly appreciated. This work was
financially supported by the post-doctoral grant of theGAČR no. 13-31276P.

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